JPH10207047A - Photosensitive solution, formation of colored image and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive solution capable of forming the colored image enhanced in the dispersibility and dispersion stability of a pigment and the uniformity of a coating film by incorporating diethylene alkyl ether acetate in an organic solvent. SOLUTION: This photosensitive solution contains a resin, the pigment, a monomer having >=1 photopolymerizable unsaturated bond in the molecule, a photoinitiator, and the organic solvent containing the diehtylene alkyl ether acetate. It is preferred that this resin has an acid value of 20-300 from a point of having alkali developability after exposure, and if the acid value is <20, the alkali developability has a tendency to drop, and if it exceeds 300, a pattern form tends to become unsharp. It is preferred that this resin has a weight average molecular weight of 1,500-200,000, and it is <1500, the dispersion stability of the pigment tends to drop and if it exceeds 200,000, the resin viscosity becomes high and its coatability lowers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive liquid for forming a colored image, a method for producing a colored image, and a method for producing a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been frequently used in liquid crystal display devices, sensors, color separation devices, and the like.
Conventionally, as a method of manufacturing this color filter, a method of patterning a dyeable resin, for example, natural gelatin or casein, and then dyeing the pattern with a dye to obtain pixels has been used. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Therefore, recently, a method of using a photosensitive material in which a pigment is dispersed has been attracting attention for the purpose of improving heat resistance and light resistance, and many studies have been made. According to this method, it is known that the manufacture is simplified, and the obtained color filter is stable and has a long life.

However, techniques for stably dispersing the pigment are difficult, and particularly, it is difficult to select an organic solvent which affects the dispersibility of the pigment. Also, if the dispersibility of the pigment is low,
When applied on a substrate, there is a problem that uneven application occurs and a color filter having a uniform color cannot be obtained. Furthermore, if the organic solvent used has a low boiling point, it tends to dry during spin coater coating, causing coating unevenness. In addition, there is a problem that the scattered photosensitive liquid dries to generate foreign matter.

[0004]

The present invention solves the above-mentioned problems of the prior art, improves the dispersibility and dispersion stability of the pigment, and significantly improves the uniformity of the coating film. It is intended to provide a photosensitive liquid for image formation. In the invention according to claim 3, the pigment in the coating film of the pixel is well dispersed,
An object of the present invention is to provide a method of manufacturing a high-quality color filter which is excellent in uniformity of a coating film of a pixel and therefore has excellent optical characteristics and good workability. The invention according to claim 4 provides a high-quality color filter in which the pigment of the coating film of the pixel is well dispersed, the uniformity of the coating film of the pixel is excellent, and the optical characteristics are excellent.

[0005]

SUMMARY OF THE INVENTION The present invention provides a resin, a pigment,
In a colored image forming photosensitive liquid containing a monomer containing one or more photopolymerizable unsaturated bonds in a molecule, a photoinitiator and an organic solvent, a colored image forming photosensitive liquid containing diethylene glycol alkyl ether acetate in an organic solvent About. The present invention also provides the colored image forming photosensitive liquid according to claim 1, wherein the resin is an resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. Liquid. Also, the present invention
The present invention relates to a method for producing a colored image including a plurality of colored image forming steps of forming a photosensitive layer prepared from the above colored image forming photosensitive liquid on a substrate and exposing and developing the photosensitive layer. The present invention also relates to a method for producing a color filter, wherein a plurality of colored images are produced on the same substrate by the method for producing a colored image.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The resin used in the photosensitive liquid for forming a colored image used in the present invention, when used as a colored image forming material, does not impair the photosensitivity, and has pigment dispersibility, film formability and developability. There is no particular limitation as long as it has As such a resin, carboxymethylhydroxyethylcellulose, cellulose resins such as hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like can be used, but methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate Acrylates or methacrylates such as acrylate, propyl acrylate, butyl acrylate, etc., homopolymers or copolymers of styrene, styrene derivatives and other polymerizable monomers, (meth) acrylic acid (mean acrylic acid and methacrylic acid The same applies hereinafter), itaconic acid,
Carboxyl group-containing polymerizable monomers such as maleic acid, maleic anhydride, and monoalkyl maleate, and (meth) acrylates, styrene, styrene derivatives,
Copolymers with other polymerizable monomers are particularly preferred.

The monoalkyl maleate is preferably one having 1 to 12 carbon atoms in the alkyl.
Monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate,
Mono n-butyl maleate, mono n-hexyl maleate, mono n-octyl maleate, mono 2-maleate
Examples include ethylhexyl, mono-n-nonyl maleate, and mono-n-dodecyl maleate. Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-
4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

Further, as the resin, a resin having a photopolymerizable unsaturated bond may be used for the purpose of improving photosensitivity and the like. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxyl group-containing resin. And one compound each having one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol Free isocyanate is added to a resin obtained by reacting a compound such as acrylamide with a compound having one ethylenically unsaturated bond (unsaturated alcohol) and a carboxyl group-containing resin having a hydroxyl group. A resin obtained by reacting an unsaturated compound having an amino group-containing compound, a resin obtained by reacting an addition reaction product of an epoxy resin and an unsaturated carboxylic acid with a polybasic acid anhydride, a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid. A resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product with an acid anhydride is exemplified. The unsaturated equivalent of these resins is preferably in the range of 600 to 3000, and more preferably in the range of 800 to 2000. If the unsaturated equivalent is too small, especially when adjusting the photosensitive material,
When the pigment is dispersed in the resin, it tends to partially cure,
If the unsaturated equivalent is too large, the improvement in photosensitivity due to the introduction of an unsaturated group tends to decrease. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

The above resin preferably has an acid value of from 20 to 300, more preferably from 40 to 200, from the viewpoint that the photosensitive layer has alkali developability after exposure. In particular, it is preferably in the range of 60 to 150. If the acid value is less than 20, alkali developability tends to decrease, and if it exceeds 300, the shape of the image pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when it is made into a photosensitive solution, and the coatability, especially the coatability when spin-coating, tends to decrease. There is. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, a resin represented by the following general formula (I)

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (II)

Embedded image (Wherein, R ³ represents an alkyl group having 1 to 12 carbon atoms, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond). The repeating unit represented by the general formula (I) / general formula (II) is 1/1 to 1
Resins having a ratio of 5/1 (molar ratio) are particularly preferred in terms of pigment dispersion stability and photosensitivity.

As a method for producing a resin having the repeating units represented by the general formulas (I) and (II), for example, the repeating units represented by the general formulas (I) and (II) may be used. Unsaturated resin (such as allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyacrylate, 2-hydroxymethacrylate, N-methylolacrylamide, etc.) A method of producing by esterification reaction, a compound having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α -Ethyl glycidyl acrylate, crotonyl glycidyl ether, Itaconic acid monoalkyl monoglycidyl ester) by addition reaction and a method of manufacturing it.

As a precursor of the resin having the repeating units represented by the general formulas (I) and (II), styrene or a derivative thereof and a monoalkyl maleate (half ester of maleic acid) are used. It can be obtained by polymerization. Examples of the styrene derivative include α-methylstyrene, m or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene, and the like. Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, and maleic acid. Mono-n-octyl, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like can be mentioned.

When the resin having the repeating unit represented by the general formula (I) or (II) is used as the resin used in the colored image forming photosensitive liquid of the present invention, other resins may be used. Resins may be used in combination. As other resins,
Among the above-mentioned resins, resins other than the resins having the repeating units represented by the above-mentioned general formulas (I) and (II) are used, and further, acrylic resins, epoxy resins, urethane resins, melamine resins, etc. May be used.
The other resin is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the resin.

Next, the pigment used in the photosensitive liquid for forming a colored image will be described. The pigment includes an inorganic pigment and an organic pigment, and any of them can be used. However, black carbon black (inorganic pigment) and an organic pigment are preferable from the viewpoint of abundant color tone. As the organic pigment, for example, azo-based,
Phthalocyanine type, indigo type, anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like can be mentioned. When producing the color filter of the present invention, each pigment system suitable for colored images such as red, green, blue and black is used. When the photosensitive liquid for forming a colored image of the present invention is used for producing a color filter, each pigment system suitable for a colored image such as red, green, blue, and black is used.

As the red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system for toning. As red pigments, for example, CI Pigment Red 9, 12 by color index name
3, 155, 168, 177, 180, 217, 22
0, 224 and the like. As a yellow pigment, for example, CI Pigment Yellow 20, 24, 83, 93, 109, 110, 117, 1
25, 139, 147, 154 and the like. These red pigment systems and yellow pigment systems may be used as a mixture of two or more types. When a mixture of a red pigment system and a yellow pigment system is used, the yellow pigment system is used.
For a total amount of 100 parts by weight of the red pigment system and the yellow pigment system,
Preferably, it is used in an amount of 50 parts by weight or less.

As a green colored image, a single green pigment system may be used, or the above-mentioned yellow pigment system may be mixed with a green pigment system to perform toning. Examples of green pigments include CI Pigment Green 7, 36, and 37 under the color index name. These green pigment system and yellow pigment system can be used as a mixture of two or more kinds. In addition, when using a mixture of a green pigment system and a yellow pigment system, the yellow pigment system is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system. .

As the blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning. As blue pigments, for example, CI Pigment Blue 15, 1
5: 3, 15: 4, 15: 6, 22, 60 and the like. Examples of purple pigments include CI Pigment Violet 19, 23, 29,
37, 50 and the like. These blue pigments and violet pigments can be used as a mixture of two or more kinds. When a mixture of a blue pigment and a violet pigment is used, the violet pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the blue pigment and the violet pigment. .

As the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron and manganese dioxide are used.

Among the monomers having one or more photopolymerizable unsaturated bonds in the molecule used in the colored image forming photosensitive solution, the monomer having one photopolymerizable unsaturated bond in the molecule is methyl methacrylate. , Butyl methacrylate, alkyl methacrylates such as 2-ethylhexyl methacrylate, alkyl acrylates such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, aralkyl methacrylates such as benzyl methacrylate, aralkyl acrylates such as benzyl acrylate, and alkoxyalkyl methacrylates such as butoxyethyl methacrylate. , Alkoxyalkyl acrylates such as butoxyethyl acrylate, aminoalkyl methacrylates such as N, N-dimethylaminoethyl methacrylate, N Aminoalkyl acrylates such as N- dimethylaminoethyl acrylate, methacrylic acid esters of (diethylene glycol ethyl ether),
Methacrylic acid esters of (polyalkylene glycol alkyl ether) such as methacrylic acid esters of (triethylene glycol butyl ether) and methacrylic acid esters of (dipropylene glycol methyl ether);
Acrylic ester of (diethylene glycol ethyl ether), (triethylene glycol butyl ether)
(Polyalkylene glycol alkyl ether) such as acrylic acid ester of (dipropylene glycol methyl ether), (polyalkylene glycol aryl ether) such as methacrylic acid ester of (hexaethylene glycol phenyl ether) Acrylates of (polyalkylene glycol aryl ethers) such as acrylates of (hexaethylene glycol phenyl ether), dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclo Decatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate, glycero Le acrylate, fluorinated alkyl methacrylates such as hepta decafluoro decyl methacrylate, fluorinated alkyl acrylates such as hept decafluoro decyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate.

Among monomers having one or more photopolymerizable unsaturated bonds in the molecule, two or more photopolymerizable unsaturated bonds in the molecule are used.
As the monomer having at least one, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned.

The monomer having two or more photopolymerizable unsaturated bonds in a molecule further includes a compound represented by the general formula (a):

Embedded image (Wherein, R represents an ethylene group or a propylene group, m and n each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A represented by the general formula (b) )

Embedded image (Where m and n are each independently 1 to 10
Epichlorohydrin modified product of bisphenol A and addition esterified product of acrylic acid, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate represented by
Glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

Embedded image (Wherein, R represents an ethylene group or a propylene group, m and n each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (d )

Embedded image (Where m and n are each independently 1 to 10
Phthalic acid modified epichlorin modified product and acrylic acid addition esterified product, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate represented by the general formula (e):

Embedded image (Where m and n are each independently 1 to 20
1,6-hexanediol and an addition esterified product of acrylic acid (having two aquilyl groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, General formula (f)

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three m's each independently represent an integer of 1 to 20), a triacrylate of an alkyne oxide adduct of phosphoric acid represented by the general formula ( g)

Embedded image (Wherein, R represents an ethylene group or a propylene group, m, m ′ and m ″ each independently represent an integer of 1 to 20). Triacrylate of an alkylene oxide adduct of trimethylolpropane , Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. These monomers may be used alone or
More than one species can be used in combination.

Examples of the photoinitiator used in the colored image forming photosensitive solution include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone,
Methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2,
-Phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photoinitiators are used alone or in combination of two or more.

It is essential that the organic solvent in the present invention contains diethylene glycol alkyl ether acetate. Examples of the diethylene glycol alkyl ether acetate include diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol iso-propyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol tert-butyl ether acetate, and the like. Among them, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol iso-propyl ether acetate and the like are preferable. These are used alone or in combination of two or more.

Further, in the photosensitive solution for forming both colored images of the present invention, other general organic solvents can be used together with diethylene glycol alkyl ether acetate as an organic solvent. The amount used is preferably 90% by weight or less based on the total amount of the organic solvent.
It is more preferred that the content be not more than% by weight. This usage is 9
If it exceeds 0% by weight, the effect of using diethylene glycol alkyl ether acetate tends to be weakened.

Examples of other organic solvents include ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds and the like. Specific examples include ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and dioxane.Alkylene glycol ether compounds include methyl cellosolve, ethyl cellosolve, butizolecellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and ethylene. Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether There are teracetate and the like, alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, tetrahydrofuran and the like, and aromatic compounds such as benzene, toluene, xylene, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone and the like.
Organic solvents such as methyl-3-methoxybutyl acetate and ethyl acetate are exemplified. These can be used alone or in combination of two or more.

The mixing ratio of the resin, pigment, monomer having two or more photopolymerizable unsaturated bonds in the molecule, and the photoinitiator used in the colored image forming photosensitive liquid is based on the total amount of these. a) The resin is preferably 10-85% by weight,
More preferably, 20 to 60% by weight, particularly preferably 25% by weight.
(B) the pigment is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 30% by weight, and (c) a photopolymerizable unsaturated bond in the molecule. The monomer having two or more is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 1 to 40% by weight.
0-30% by weight, (d) the photoinitiator is preferably 0.0
The content is 1 to 20% by weight, more preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.

If the amount of the resin in the colored image forming photosensitive liquid is too small, the dispersion stability of the pigment tends to decrease. If the amount is too large, the viscosity of the photosensitive liquid becomes high, and the coating properties, especially spin coating, are increased. In this case, the applicability tends to decrease. When the amount of the pigment is too small, the color density of the image tends to be low, and when the amount is too large, the light sensitivity tends to be low. When the amount of the monomer having two or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to decrease, and when the amount is too large, the dispersion stability of the pigment tends to decrease. Furthermore, when the photoinitiator is too small, the photosensitivity tends to decrease, and when too large, the adhesion tends to decrease.

The organic solvent has a total solid content of 5 to 40% by weight including a resin, a pigment, a monomer containing one or more photopolymerizable unsaturated bonds in a molecule and a photoinitiator in the photosensitive solution. It is preferably used as follows. If the total solid content exceeds 40% by weight, the viscosity tends to be high and the applicability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

The photosensitive solution for forming a colored image of the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-
Butyl catechol, etc.), titanate coupling agents for improving adhesion to a substrate (a silane coupling agent having a vinyl group, an epoxy group, an amino group, a mercapto group, etc., isopropyl trimethacryloyl titanate,
Various additives such as diisopropylisostearoyl-4-aminobenzoyl titanate), surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) for improving the smoothness of the film, and other ultraviolet absorbers and antioxidants The agent can be appropriately used as needed.

Next, a method for producing the photosensitive liquid for forming a colored image used in the present invention will be described. The pigment is mixed and dispersed with a resin, an organic solvent, and, if necessary, a dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. The monomer having two or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator may be mixed before or after the dispersion treatment.

Examples of the dispersant include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, and nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers. An organic dye derivative such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacdrine-based organic dye into which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced. It is preferable because the dispersibility and dispersion stability of the pigment are improved. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

In the above-mentioned dispersion treatment, the whole amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease. Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, the organic solvent is
It is preferable to use at least 100 parts by weight at the time of the dispersion treatment based on 100 parts by weight of the total amount of the pigment and the resin at the time of the dispersion treatment. If the amount is less than 100 parts by weight, the viscosity at the time of the dispersion treatment is too high, and particularly when the dispersion is performed by a ball mill, a sand mill, a bead mill or the like, the dispersion may be difficult.

In order to laminate a photosensitive layer on a substrate using the colored image forming photosensitive liquid according to the present invention, the photosensitive liquid is applied directly to the substrate or the photosensitive liquid is applied to a support once to form a film. After that, it can be performed by laminating on a substrate or the like. The above substrate is selected depending on the application,
For example, white plate glass, blue plate glass, transparent glass plate such as silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, synthetic resin sheet such as vinyl chloride resin, film or plate, aluminum plate, copper plate,
Examples include a metal plate such as a nickel plate and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium evaporation or the like.

The method of applying the photosensitive liquid to the substrate includes roll coater coating, spin coater coating, spray coating, wicker coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and the like. There is.
After application, it is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Thus, a film composed of the colored image forming material can be obtained. The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is preferably 0.1 to 3 mm.
It is preferably in the range of 00 μm. When used for a color filter, the thickness is preferably in the range of 0.2 to 5 μm.

A photosensitive layer can be formed on a support in the same manner as described above. In order to laminate the photosensitive layer on the substrate, there is a method in which a film is laminated on the substrate and pressure-bonded through a roller. At this time, it is preferable to slightly heat the roller. Further, it is preferable to perform the pressure bonding under reduced pressure. The support is preferably peeled off after the photosensitive layer is laminated on the substrate. As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used.

The exposure of the photosensitive layer laminated on the substrate can be performed by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above. As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a Langsten lamp, a visible light laser and the like are suitable. Using these light sources, actinic rays are irradiated imagewise by pattern exposure through a photomask, direct drawing by scanning, or the like.

Following the above exposure, a development step is performed. An aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine, or a salt. (Alkaline developer), a non-exposed portion is removed by spraying a developer such as an organic solvent or dipping in a developer to obtain a colored image pattern of a cured film corresponding to an image. After development, post-baking is preferably performed to further harden the colored image pattern. The post-bake temperature is preferably from 60 to 280C, and the heating time is preferably from about 1 to 60 minutes.

A colored image is formed by such a colored image forming process. In particular, in a method of manufacturing a color filter, it is preferable to repeat the colored image forming process for three to four different colored images. In the present invention, three to four different colored images are three colors of red, green, and blue when a red, green, and blue colored image is formed on a black matrix previously formed by chromium evaporation or the like. Means a colored image, after forming a black matrix using a black colored image forming material, red, green, when forming a blue colored image, or red, green, after forming a blue colored image, When forming a black matrix using a black image forming material in the gap between these colored images,
It means four colored images of black, red, green and blue. Red-green,
The order of forming the blue colored image is arbitrary. The colored image is adapted to form pixels for each color.

[0040]

The present invention will be described below with reference to examples. (1) Resin used: 50 mol% of styrene-20 mol% of maleic acid monopropyl ester-maleic acid derivative 3
A copolymer composed of 0 mol%, having a weight average molecular weight of 11,000 and an acid value of 65 (hereinafter referred to as copolymer A). (2) The maleic acid derivative has the following structure.

Embedded image

Example 1 10 g of copolymer A as a resin and 38 g of carbon black as a pigment were added to 200 g of diethylene glycol ethyl ether acetate as an organic solvent, and dispersed in a bead mill for 2 hours. To this dispersion was added trimethylolpropane triacrylate 32 as a monomer.
g, 12 g of benzophenone as a photoinitiator and N, N '
-Tetraethyl-4,4'-diaminobenzophenone 4
g and 100 g of diethylene glycol monoethyl ether acetate as an organic solvent were added and mixed to obtain a black colored image forming photosensitive liquid. The obtained photosensitive solution was added to 25
The number of days until secondary aggregation started when the sample was allowed to stand at 0 ° C. was defined as dispersion stability, and the results are shown in Table 1. Further, the obtained photosensitive liquid was used for a glass substrate (manufactured by Corning, trade name 705)
9) After spin-coating, the film was dried at 110 ° C. for 5 minutes to form a film having a thickness of 1.0 μm, and the appearance of the coated film was visually evaluated. The results are shown in Table 1.

The resulting film was imagewise exposed to light of 600 mJ / cm ² by means of an ultra-high pressure mercury lamp through a negative mask, and then 0.5% of polyoxyethylene nonylphenyl ether (Nonal 912A, manufactured by Toho Chemical Co., Ltd.) was added. weight%
And an aqueous solution containing 0.3% by weight of potassium hydroxide,
Development was performed to obtain a black image pattern. The optical density of the obtained black image pattern was 2.5. Also,
The light sensitivity, resolution, and pattern shape of the obtained black image pattern were evaluated by the following test methods, and the results are shown in Table 1.

Test Method Light sensitivity: The optical density was evaluated as the first step, using a 21-step step tablet in which the optical density increased by 0.15 for each step. The larger the value, the better the light sensitivity. Resolution: Evaluated using a negative mask having a pattern having the same line and space width (μm). It is indicated by the minimum line and space width (μm) that could be completely developed, and the smaller the value, the better the resolution. Pattern shape: The surface state and cross-sectional shape of the image pattern were evaluated. The more uniform the surface and the nearer the cross-sectional shape is, the better the pattern shape becomes.

Example 2 30 g of copolymer A as a resin, 21 g of CI Pigment Red 177 by a color index name as a pigment, and 21 g of a pigment
4 g of CI Pigment Yellow 139 and diethylene glycol ethyl ether acetate 200 as an organic solvent
g of the solvent, and this was dispersed for 2 hours using a bead mill. To this dispersion, 32 g of pentaerythritol tetraacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-4,4'-
2 g of diaminobenzophenone and 100 g of organic solvent diethylene glycol ethyl ether acetate were added and mixed to obtain a red colored image forming photosensitive liquid. The obtained photosensitive liquid was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 1. In addition, the obtained photosensitive solution is
A film having a thickness of 1.7 μm was formed in the same manner as in Example 1.
The appearance of the coating film at the time of application was visually evaluated, and the results are shown in Table 1.
It was shown to.

The resulting film was imagewise exposed to light of 100 mJ / cm ² by means of an ultra-high pressure mercury lamp through a negative mask, and then 0.5 g of polyoxyethylene nonylphenyl ether (Nonal 912A, manufactured by Toho Chemical Co., Ltd.) was added. weight%
And an aqueous solution containing 0.3% by weight of potassium hydroxide,
Development was performed to obtain a black image pattern. The light sensitivity, resolution, and pattern shape of the obtained red image pattern were evaluated by the same test method as in Example 1, and the results are shown in Table 1.

Example 3 40 g of copolymer A as a resin, 15 g of CI Pigment Green 36 by a color index name as a pigment, and
5 g of CI Pigment Yellow 83 and 200 g of diethylene glycol ethyl ether acetate as an organic solvent
Was dispersed using a bead mill for 2 hours. To this dispersion, 32 g of trimethylolpropane triacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and 100 g of diethylene glycol ethyl ether acetate as an organic solvent were added and mixed. Thus, a green colored image forming photosensitive liquid was obtained. The obtained photosensitive liquid was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 1. Further, the obtained photosensitive solution was used in Example 2
In the same manner as in the above, a film was formed, and the appearance of the coated film when applied was visually evaluated. The results are shown in Table 1.

The obtained film was exposed and developed in the same manner as in Example 2 to obtain a green image pattern. The light sensitivity, resolution, and pattern shape of the obtained green image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 40 g of copolymer A as a resin, 17 g of CI Pigment Blue 15-6 as a pigment and 1 g of CI Pigment Violet 23 as a pigment, and diethylene glycol ethyl ether acetate 2 as an organic solvent were used.
In addition to this, this was dispersed for 2 hours using a bead mill. 34 g of pentaerythritol tetraacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator, and diethylene glycol ethyl as an organic solvent other than an essential component in the organic solvent. 100 g of ether acetate was added and mixed to obtain a blue colored image forming photosensitive liquid. The obtained photosensitive liquid was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 1.
Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 2, and the appearance of the coating film when applied was visually evaluated. The results are shown in Table 1.

The obtained film was exposed in the same manner as in Example 2, and then developed with an aqueous solution containing 1% by weight of sodium carbonate to obtain a blue image pattern. The light sensitivity, resolution, and pattern shape of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A black colored image forming photosensitive liquid was obtained in the same manner as in Example 1 except that the organic solvent was changed to ethylene glycol monoethyl ether. The obtained photosensitive liquid was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 1. Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the appearance of the coating film when applied was visually evaluated. The results are shown in Table 1. The obtained film was exposed and developed in the same manner as in Example 1 to obtain a green image pattern. The light sensitivity, resolution, and pattern shape of the obtained green image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A blue colored image forming photosensitive liquid was obtained in the same manner as in Example 1 except that all of the organic solvent was changed to diethylene glycol diethyl ether. The obtained photosensitive liquid was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 1. Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the appearance of the coating film when applied was visually evaluated. The results are shown in Table 1. The obtained film was exposed and developed in the same manner as in Example 1 to obtain a blue image pattern. The light sensitivity, resolution, and pattern shape of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 A red colored image forming photosensitive liquid was obtained in the same manner as in Example 2 except that the organic solvent was changed to ethylene glycol monoethyl ether. The obtained photosensitive solution was evaluated for dispersion stability in the same manner as in Example 2, and the results are shown in Table 1. Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the appearance of the coating film when applied was visually evaluated. The results are shown in Table 1. The obtained film was exposed and developed in the same manner as in Example 2 to obtain a green image pattern. The light sensitivity, resolution, and pattern shape of the obtained green image pattern were evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 4 A red colored image forming photosensitive liquid was obtained in the same manner as in Example 2 except that all organic solvents were changed to diethylene glycol diethyl ether. The obtained photosensitive solution was evaluated for dispersion stability in the same manner as in Example 2, and the results are shown in Table 1. Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the appearance of the coating film when applied was visually evaluated. The results are shown in Table 1. The obtained film was exposed and developed in the same manner as in Example 2 to obtain a green image pattern. The light sensitivity, resolution, and pattern shape of the obtained green image pattern were evaluated in the same manner as in Example 2, and the results are shown in Table 1.

[0054]

[Table 1]

From Table 1, it can be seen that the photosensitive liquids for forming a colored image (Comparative Examples 1 and 3) prepared using an organic solvent outside the range of the organic solvent in the present invention have a low dispersion stability of the pigment. Secondary aggregation began within 10 days. In addition, the appearance of the coating film when these liquids were applied was poor due to uneven coating occurring everywhere. Similarly, the photosensitivity of the coating film was poor, the sensitivity and resolution were low, and there was a problem with the obtained pattern shape. In Comparative Examples 2 and 4, the dispersion stability of the pigment was good, and there was no problem with the photosensitivity. However, when applied by the spin coating method, drying was fast, and uneven application was observed at corners of the substrate. Occurred and the appearance of the coating film was poor. In contrast, the photosensitive liquids for forming a colored image (Examples 1, 2, 3, and 4) prepared using the organic solvent according to the present invention have high dispersion stability of the pigment, and are left for 90 days or more after the liquid preparation. No secondary aggregation occurred. The appearance of the coating film when these liquids were applied was extremely uniform and good. Similarly, the photosensitivity of the coating film was good, the sensitivity and the resolution were both high, and the obtained pattern shape was rectangular and good.

Example 5 After a black matrix was formed from chromium on the glass substrate used in Example 1, a red image pattern was formed in the same manner as in Example 2, and post-heating was performed at 240 ° C. for 10 minutes. Was done. Next, using the substrate, a green image pattern was formed next to the red image pattern in the same manner as in Example 3, and post-heating was performed at 240 ° C. for 10 minutes. Next, using the substrate, a blue image pattern is formed next to the green image pattern in the same manner as in Example 4.
Post-heating was performed at 40 ° C. for 10 minutes. Thus, a high-quality color filter in which one pixel is composed of three colors of red, green, and blue of 30 μm × 100 μm and in which the pixels are arranged in a mosaic shape was manufactured.

Example 6 A black image pattern (black matrix) was formed on the glass substrate used in Example 1 in the same manner as in Example 1, and post-heating was performed at 240 ° C. for 10 minutes. Next, pixels are formed in the order of red, green and blue in the same manner as in Example 5, and one pixel is formed of 30 μm × 100 μm red,
A high-quality color filter having pixels arranged in a mosaic of three colors of green and blue was produced.

As in Examples 5 and 6, the color filters prepared by using a photosensitive liquid having a better dispersion stability than ever before have excellent depolarizing properties of 1000 or more, exhibit excellent optical characteristics, and are suitable for image display. It was confirmed that the device was excellent.

[0059]

According to the first or second aspect of the present invention, the photosensitive liquid for forming a colored image has high dispersibility and dispersion stability of the pigment, from which a film having an excellent appearance can be obtained. According to the manufacturing method of the third aspect, the pigment of the coating film of the pixel is well dispersed, and the uniformity of the coating film of the pixel is excellent, so that a high-quality colored image having excellent optical characteristics can be manufactured. According to the production method of claim 4, a color filter having a good dispersion of the pigment of the coating film of the pixel, excellent uniformity of the coating film of the pixel, and therefore having excellent optical characteristics, high quality, and excellent as an image display element. Obtainable.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/033 G03F 7/033 (72) Inventor Seigo Yokochi 14 Goi Minamikaigan, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Plant (72) Inventor Tetsuya Okazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant of Hitachi Chemical Co., Ltd. (72) Inventor Shinya Kato 14 Goi South Coast, Ichihara City, Chiba Prefecture 14 Goi Plant of Hitachi Chemical Co., Ltd. (72) Inventor Tomohiro Nagoya 14 Goi South Coast, Ichihara City, Chiba Pref.Hitachi Chemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A colored image forming photosensitive liquid containing a resin, a pigment, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, a photoinitiator and an organic solvent, wherein the diethylene glycol alkyl ether is contained in the organic solvent. A photosensitive liquid for forming a colored image containing acetate. 2. The colored image forming photosensitive liquid according to claim 1, wherein the resin has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. 3. A method for producing a colored image, comprising a step of laminating a photosensitive layer prepared from the photosensitive liquid for forming a colored image according to claim 1 on a substrate, and exposing and developing the layer. 4. A method for producing a color filter, wherein a plurality of colored images are produced on the same substrate by the method for producing a colored image according to claim 3.